EP3168847A1 - Photoelektrisches umwandlungselement, farbstoffsensibilisierte solarzelle, metallkomplexfarbstoff, farbstofflösung und terpyridin-verbindung oder veresterungsprodukt davon - Google Patents

Photoelektrisches umwandlungselement, farbstoffsensibilisierte solarzelle, metallkomplexfarbstoff, farbstofflösung und terpyridin-verbindung oder veresterungsprodukt davon Download PDF

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Publication number: EP3168847A1
Authority: EP; European Patent Office
Prior art keywords: ring; group; formula; dye; substituent
Prior art date: 2014-07-07
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP15818813.6A

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English (en)

French (fr)

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EP3168847A4 (de

EP3168847B1 (de

Inventor

Kazuhiro TSUNA

Kousuke Watanabe

Katsumi Kobayashi

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Fujifilm Corp

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Fujifilm Corp

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2014-07-07

Filing date

2015-07-01

Publication date

2017-05-17

2015-07-01 Application filed by Fujifilm Corp filed Critical Fujifilm Corp

2017-05-17 Publication of EP3168847A1 publication Critical patent/EP3168847A1/de

2017-05-31 Publication of EP3168847A4 publication Critical patent/EP3168847A4/de

2018-05-16 Application granted granted Critical

2018-05-16 Publication of EP3168847B1 publication Critical patent/EP3168847B1/de

Status Not-in-force legal-status Critical Current

2035-07-01 Anticipated expiration legal-status Critical

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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells

Definitions

the present invention relates to a photoelectric conversion element, a dye-sensitized solar cell, a metal complex dye, a dye solution, and a terpyridine compound or an esterified product thereof.
Photoelectric conversion elements are used in various photosensors, copying machines, photoelectrochemical cells such as solar cells, and the like. These photoelectric conversion elements have adopted various systems to be put into use, such as systems utilizing metals, systems utilizing semiconductors, systems utilizing organic pigments or dyes, or combinations of these elements.
solar cells utilizing inexhaustible solar energy do not necessitate fuels, and full-fledged practicalization of solar cells as an inexhaustible clean energy is being highly expected.
silicon-based solar cells has long been in progress, and many countries also support policy-wise considerations, and thus dissemination of silicon-based solar cells is still in progress.
silicon is an inorganic material, and thus, naturally has limitations in terms of improvement of throughput, cost, and the like.
dyes called N3, N719, N749 also referred to as Black Dye
Z907, and J2 have generally been developed as metal complex dyes for use in dye-sensitized solar cells.
all of the photoelectric conversion elements and dye-sensitized solar cells using these dyes are not sufficient in terms of photoelectric conversion efficiency and durability (heat stability).
JP2013-229285A describes a metal complex dye having a terpyridine ligand in which one thiophene ring group is bonded at the 3-position with respect to the ring-constituting nitrogen atom coordinating to a metal ion of a terminal pyridine ring, and a doner ligand having a cyclic group substituted with a specific substituent. It also describes that a photoelectrochemical cell using the metal complex dye accomplishes both of reduction in performance irregularity and improvement of photoelectric conversion efficiency and durability.
a layer (also referred to as a semiconductor layer) which is formed of semiconductor fine particles and carries a metal complex dye is usually formed into a layer with a thickness of 10 to several hundred ⁇ m.
a layer also referred to as a semiconductor layer
reduction in thickness (size) and weight has been required.
the photoelectric conversion efficiency varies depending on the film thickness of a semiconductor layer, and tends to decrease as the film thickness becomes smaller. Accordingly, excellent photoelectric conversion efficiency is required to be exhibited even in a case where the film thickness of the semiconductor layer is small.
the present invention has an object to provide a photoelectric conversion element and a dye-sensitized solar cell, each of which is less affected by the film thickness of a semiconductor layer, exhibits excellent photoelectric conversion efficiency, particularly even when the film thickness is small, and has high durability; and a metal complex dye, a dye solution, and a terpyridine compound or an esterified product thereof, each of which is used in the photoelectric conversion element and the dye-sensitized solar cell.
the present inventors have discovered that when a combination of a tridentate ligand with a terminal portion having a nitrogen-containing aromatic ring in which a plurality of thiophene ring groups are introduced to a ring-constituting atom at the 4-position with respect to a coordinating atom by linkage, with a bidentate or tridentate ligand which coordinates to a metal ion through at least one nitrogen atom and an anion of at least one atom is used in a metal complex dye for use in a photoelectric conversion element and a dye-sensitized solar cell, it is possible to realize further improvement of photoelectric conversion efficiency and durability as well as high photoelectric conversion efficiency even when the semiconductor layer is a thin film. Based on these findings, the present invention has been completed.
the double bond may be either one of the two configurations or a mixture thereof.
Examples of the aliphatic hydrocarbon ring include a saturated hydrocarbon ring, and an unsaturated hydrocarbon ring not exhibiting aromaticity, for example, a saturated monocyclic hydrocarbon ring (cycloalkane), a saturated polycyclic hydrocarbon ring, an unsaturated monocyclic hydrocarbon ring (cycloalkene and cycloalkyne), and an unsaturated polycyclic hydrocarbon ring.
a saturated monocyclic hydrocarbon ring cycloalkane
a saturated polycyclic hydrocarbon ring saturated polycyclic hydrocarbon ring
an unsaturated monocyclic hydrocarbon ring cycloalkene and cycloalkyne
expressions of a compound are used to mean inclusion of, in addition to the compound itself, salts and ions of the compound. Further, within a range exhibiting desired effects, the expressions are used to mean inclusion of modifications of a part of the structure.
a compound in which substitution or non-substitution is not explicitly described is used to mean the inclusion of compounds which have an arbitrary substituent within a range exhibiting the desired effects. This also applies to substituents, linking groups, and ligands.
a numerical value range represented by "(a value) to (a value)” means a range including the numerical values indicated before and after “to” as a lower limit value and an upper limit value, respectively.
the photoelectric conversion element and the dye-sensitized solar cell of the present invention have a metal complex dye using a combination of a tridentate ligand with a terminal portion having a nitrogen-containing aromatic ring in which a plurality of thiophene ring groups are introduced to a ring-constituting atom at the 4-position with respect to a coordinating atom by linkage, with a bidentate or tridentate ligand which coordinates to a metal ion through at least one nitrogen atom and an anion of at least one atom.
a metal complex dye using a combination of a tridentate ligand with a terminal portion having a nitrogen-containing aromatic ring in which a plurality of thiophene ring groups are introduced to a ring-constituting atom at the 4-position with respect to a coordinating atom by linkage, with a bidentate or tridentate ligand which coordinates to a metal ion through at least one nitrogen atom and an
a photoelectric conversion element and a dye-sensitized solar cell each of which is less affected by the film thickness of a semiconductor layer, exhibits excellent photoelectric conversion efficiency, particularly when the film thickness is small, and has high durability; and a metal complex dye, a dye solution, and a terpyridine compound or an esterified product thereof, each of which is used in the photoelectric conversion element and the dye-sensitized solar cell.
the photoelectric conversion element of the present invention has an electrically conductive support, a photoconductor layer including an electrolyte, a charge transfer layer including an electrolyte, and a counter electrode (opposite electrode).
the photoconductor layer, the charge transfer layer, and the counter electrode are provided in this order on the electrically conductive support.
the semiconductor fine particles forming the photoconductor layer carries a metal complex dye represented by Formula (I) which will be described later, as a sensitizing dye.
the aspect in which the metal complex dye is carried on the surface of the semiconductor fine particles encompasses an aspect in which the metal complex dye is deposited on the surface of the semiconductor fine particles, an aspect in which the metal complex dye is adsorbed onto the surface of the semiconductor fine particles, and a mixture of the aspects.
the adsorption includes chemical adsorption and physical adsorption, with the chemical adsorption being preferable.
the semiconductor fine particles may carry other metal complex dyes, together with the metal complex dye of Formula (I) which will be described later.
the semiconductor fine particles preferably carry a co-adsorbent which will be described later, together with the metal complex dye.
the photoconductor layer includes an electrolyte.
the electrolyte included in the photoconductor layer may be the same as or different from the electrolyte included in the charge transfer layer, but they are preferably the same.
the expression “electrolytes are the same” is used to mean inclusion of both of an aspect in which the components included in the electrolyte of the photoconductor layer are the same as the components included in the electrolyte of the charge transfer layer and the contents of both the components are the same, and an aspect in which the components included in the electrolyte of the photoconductor layer are the same as the components included in the electrolyte of the charge transfer layer but the contents of both the components are different.
the photoelectric conversion element of the present invention is not particularly limited in terms of configurations other than the configuration defined in the present invention, and may adopt known configurations regarding photoelectric conversion elements.
the respective layers constituting the photoelectric conversion element of the present invention are designed depending on purposes, and may be formed into, for example, a single layer or multiple layers. Further, layers other than the layers may be included, as necessary.
the dye-sensitized solar cell of the present invention is formed by using the photoelectric conversion element of the present invention.
the photoelectric conversion element 10 includes semiconductor fine particles 22 sensitized by carrying an electrically conductive support 1 and a dye (metal complex dye) 21, a photoconductor layer 2 including an electrolyte between the semiconductor fine particles 22, a charge transfer layer 3 that is a hole transport layer, and a counter electrode 4.
semiconductor fine particles 22 sensitized by carrying an electrically conductive support 1 and a dye (metal complex dye) 21, a photoconductor layer 2 including an electrolyte between the semiconductor fine particles 22, a charge transfer layer 3 that is a hole transport layer, and a counter electrode 4.
the light-receiving electrode 5 has the electrically conductive support 1 and the photoconductor layer 2, and functions as a functional electrode.
a dye-sensitized solar cell 20 shown in Fig. 2 is constituted with a photoelectric conversion element in the second aspect of the present invention.
the photoelectric conversion element which becomes the dye-sensitized solar cell 20 is different in the configurations of the electrically conductive support 41 and the photoconductor layer 42, and also differs in that it has a spacer S, but except for these, has the same structure as the photoelectric conversion element 10 shown in Fig. 1 . That is, the electrically conductive support 41 has a bilayered structure including a substrate 44 and a transparent electrically-conductive film 43 which is formed on the surface of the substrate 44. Further, the photoconductor layer 42 has a bilayered structure including a semiconductor layer 45 and a light-scattering layer 46 which is formed adjacent to the semiconductor layer 45. A spacer S is provided between the electrically conductive support 41 and the counter electrode 48. In the dye-sensitized solar cell 20, 40 is a light-receiving electrode, and 47 is a charge transfer layer.
the dye-sensitized solar cell 20 functions as a solar cell by light incident on the photoconductor layer 42.
the photoelectric conversion element and the dye-sensitized solar cell of the present invention are not limited to the above preferred aspects, and the configuration of each of the aspects can be combined as appropriate within a range not departing from the scope of the present invention.
the materials and the respective members for use in the photoelectric conversion element and the dye-sensitized solar cell can be prepared by ordinary methods.
the metal complex dye of the present invention is represented by the following Formula (I).
the metal complex dye of the present invention is less affected by a change in the film thickness of a semiconductor layer, and can impart high photoelectric conversion efficiency and excellent heat stability to the photoelectric conversion element and the dye-sensitized solar cell by including a ligand LA represented by the following Formula (AL-1). Accordingly, the metal complex dye of the present invention is preferably used as a sensitizing dye in a dye-sensitized solar cell.
Za and Zb each independently represent a non-metal atomic group necessary for forming a 5- or 6-membered ring, in which at least one of rings formed by Za and Zb, respectively, has one or more acidic groups, L w 's each independently represent a nitrogen atom or CR w , and R w represents a hydrogen atom or a substituent.
G represents a group represented by any one of the following Formulae (X-1) to (X-3), n represents an integer of 2 to 7, T represents a hydrogen atom or a substituent, and a -(G)n-T group does not have an acidic group and an amino group.
Zt2 and Zt3 each represent a non-metal atomic group necessary for forming a fused ring with a thiophene ring in Formula (X-2) or (X-3).
* represents a binding position to a ring including L w , or another G or T.
LD represents a bidentate ligand, or a tridentate ligand different from LA.
LX represents a monodentate ligand.
mX represents 1, and when LD is a tridentate ligand, mX represents 0.
CI represents a counterion necessary for neutralizing the charge of the metal complex dye
mY represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
M is a central metal ion of the metal complex dye, and examples thereof include ions of elements belonging to Groups 6 to 12 on the long-form periodic table of the elements.
metal ions include respective ions of Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn, and Zn.
the metal ion M may be one kind of ion, or two or more kinds of ions.
the metal ion M is preferably Os 2+ , Ru 2+ , or Fe 2+ , more preferably Os 2+ or Ru 2+ , and among these, Ru 2+ is particularly preferable.
the valence of M may be changed by the redox reaction with the surrounding material.
the ligand LA is a tridentate ligand or compound which is represented by Formula (AL-1) and coordinates to a metal ion M through three nitrogen atoms in Formula (AL-1).
This ligand LA has at least one acidic group (also referred to as an adsorptive group) on at least one of the ring formed by Za and the ring formed by Zb, each of which will be described later.
the ligand LA is a ligand which makes the metal complex dye of the present invention carried on the semiconductor fine particles.
the ligand LA has a "-(G)n-T" group on the ring-constituting carbon atom at the 4-position with respect to a ring-constituting nitrogen atom that coordinates to a metal ion M of a ring formed of a nitrogen atom, a carbon atom, and L w (also referred to as a terminal nitrogen-containing ring or a hetero ring including L w ). It is thought that in the ligand LA, if the "-(G)n-T" group is bonded to the ring-constituting carbon atom at the 4-position of the hetero ring including L w , the absorbance of a metal complex dye having the ligand LA increases.
a photoelectric conversion element and a dye-sensitized solar cell each containing the metal complex dye having enhanced absorbance in the photoconductor layer, have improved photoelectric conversion efficiency. Further, even when the film thickness of a semiconductor layer that will provide a photoconductor layer is small, excellent photoelectric conversion efficiency is exhibited. Moreover, the durability of the photoelectric conversion element and the dye-sensitized solar cell is also improved. Accordingly, this ligand LA is preferably used as a ligand of a metal complex dye for use in a dye-sensitized solar cell.
Za and Zb each independently represent a non-metal atomic group necessary for forming a 5-membered ring or a 6-membered ring.
Za and Zb are each preferably a non-metal atomic group selected from a carbon atom and the heteroatoms, and more preferably a non-metal atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
the rings formed by Za and Zb are preferably an aromatic hetero ring as a 5-membered ring and an aromatic hetero ring as a 6-membered ring. These rings encompass a monocycle as well as a fused ring formed by the fusion of at least one of an aromatic ring or an aliphatic ring to the monocycle. Further, the ring formed by Za and the ring formed by Zb may have a substituent, which is preferably selected from the substituent group T R which will be described later, and a fused ring formed by the mutual bonding of the rings through this substituent may be formed. Examples of such a fused ring include a 1,10-phenanthroline ring.
the aromatic hetero ring as a 5-membered ring may be any one of 5-membered rings including the heteroatom as a ring-constituting atom. It is preferably, for example, at least one of a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring.
the aromatic hetero ring as a 6-membered ring may be any one of 6-membered rings including the heteroatom as a ring-constituting atom.
a pyridine ring preferably, for example, at least one of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, and an isoquinoline ring.
the rings formed by Za and Zb are each at least one selected from the group consisting of the group including the aromatic hetero rings as a 5-membered ring and the group including the aromatic hetero rings as a 6-membered ring, and aromatic hetero rings which are suitable for the structures of the respective rings represented by Formula (AL-1) are preferably selected.
the ring formed by Za is preferably at least one selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a pyrazole ring, a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring.
the ring formed by Zb is preferably at least one selected from the group consisting of a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a tetrazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a triazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, and a benzothiazole ring.
G that forms the group is a thiophene ring, or a thiophene-containing fused ring, and is represented by any one of the following Formulae (X-1) to (X-3).
the thiophene ring group represented by Formula (X-1) may have a substituent R T1 .
the substituent R T1 include a group (excluding an amino group) selected from the substituent group T R which will be described later.
the substituent R T1 is preferably an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an arylthio group, a cycloalkyl group, an aryl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, a cyano group, or a halogen atom.
an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an arylthio group, and an aryloxy group are more preferable; an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, and an alkylthio group are still more preferable; and an alkyl group is particularly preferable.
the number of carbon atoms in the alkyl group that can be adopted as R T1 is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 9.
the substitution position is not particularly limited.
the number PT1 of the substituents R T1 is 0 to 2, and preferably 0 or 1.
* represents a binding position to a ring including L w , or another G or T.
the binding position of the thiophene ring group represented by Formula (X-1) is not particularly limited, and may be any one of the ring-constituting carbon atoms. It is preferable that at least one binding position is the 2-position with respect to the ring-constituting sulfur atom.
Zt2 represents a non-metal atomic group necessary for forming a fused ring with the thiophene ring in Formula (X-2).
the non-metal atomic group is selected from a carbon atom, a hydrogen atom, and the heteroatoms, according to the thiophene-containing fused ring group represented by Formula (X-2).
the thiophene-containing fused ring group represented by Formula (X-2) is a fused ring group formed by the fusion of at least one aromatic ring or aliphatic ring with the ring-constituting carbon atoms at the 2- and 3-positions with respect to the ring-constituting sulfur atom in the thiophene ring in Formula (X-2).
the ring to be fused with the thiophene ring is not particularly limited, but is preferably an aromatic ring or an aliphatic hetero ring, and more preferably an aromatic hetero ring. Further, the ring to be fused is not particularly limited, but is preferably a 5- or 6-membered ring, and more preferably a 5-membered ring.
Examples of such a ring include a pyrrole ring, a thiophene ring, a furan ring, a silole ring, a phosphole ring, and a selenophene ring.
a thiophene ring, a furan ring, and a silole ring are preferable, and a thiophene ring is more preferable.
the number of rings (including the thiophene rings in the formula) that form the thiophene-containing fused ring group represented by Formula (X-2) is not particularly limited, but is preferably 2 to 5, and more preferably 2 or 3.
the thiophene-containing fused ring group represented by Formula (X-2) may have a substituent R T2 .
the substituent R T2 has the same definition as the substituent R T1 , and preferred examples thereof are is also the same.
the substitution position is not particularly limited.
the substituent R T2 may be bonded to the ring-constituting carbon atom of the thiophene ring, or may be bonded to the ring-constituting carbon atom of a ring to be fused.
the number PT2 of the substituents R T2 contained in the thiophene-containing fused ring group is an integer of 0 or more.
the upper limit is no more than the number of hydrogen atoms contained in the fused ring group when the thiophene-containing fused ring group represented by Formula (X-2) is unsubstituted. If PT2 falls within the range, it is not particularly limited, but is preferably 0 to 2, and more preferably 0 or 1.
the binding position of the thiophene-containing fused ring group represented by Formula (X-2) is not particularly limited, and may by any one of the ring-constituting carbon atoms. Preferably, at least one binding position is the 2-position with respect to the ring-constituting sulfur atom.
Zt3 represents a non-metal atomic group necessary for forming a fused ring with the thiophene ring in Formula (X-3).
the non-metal atomic group is selected from a carbon atom, a hydrogen atom, and the heteroatom, according to the thiophene-containing fused ring group represented by Formula (X-3).
the thiophene-containing fused ring group represented by Formula (X-3) is a fused ring group formed by the fusion of at least one aromatic ring or aliphatic ring with the ring-constituting carbon atoms at the 3- and 4-positions with respect to the ring-constituting sulfur atom in the thiophene ring in Formula (X-3).
a first aspect of the ring fused with the thiophene ring has the same definition as the ring fused with the thiophene ring in Formula (X-2), and preferred examples thereof are also the same.
a second aspect is an aliphatic hetero ring formed by the bonding of an alkylenedioxy group or alkylenedithio group at the 3-and 4-positions of the thiophene ring in Formula (X-3) to the ring-constituting carbon atom.
an alkylenedioxy group is preferable, and examples thereof include ethylenedioxy and propylenedioxy.
the number of rings (including the thiophene ring in the formula) that form the thiophene-containing fused ring group represented by Formula (X-3) is not particularly limited, but is preferably 2 to 4, and more preferably 2.
the thiophene-containing fused ring group represented by Formula (X-3) may have a substituent R T3 .
the substituent R T3 has the same definition as the substituent R T1 , and preferred examples thereof are is also the same.
the substitution position is not particularly limited.
the substituent may be bonded to the ring-constituting carbon atom of the thiophene ring, or may be bonded to the ring-constituting carbon atom of the ring to be fused.
the number PT3 of the substituents R T3 contained in the thiophene-containing fused ring group is an integer of 0 or more.
the upper limit is no more than the number of hydrogen atoms contained in the fused ring group when the thiophene-containing fused ring group represented by Formula (X-3) is unsubstituted. If PT3 falls within the range, it is not particularly limited, but is preferably 0 to 2, and more preferably 0 or 1.
the binding position of the thiophene-containing fused ring group represented by Formula (X-3) is not particularly limited, and may by any one of the ring-constituting carbon atoms. Preferably, at least one binding position is the 2-position with respect to the ring-constituting sulfur atom.
the thiophene ring group represented by Formula (X-1) is preferably a ring group represented by any one of the following Formulae (X-1a) to (X-1c).
R T1a to R T1c each independently represent a hydrogen atom or a substituent.
the substituent has the same definition as R T1 in Formula (X-1), and preferred examples thereof are is also the same.
R T1a and R T1b , and R T1b and R T1c may each be bonded to each other to form a ring.
** represents a binding position to a ring including L w , or another G or T.
any one of two **'s may be bonded to the ring including L w or to G adjacent to the side of the ring including L w .
the thiophene ring group represented by Formula (X-1a) is preferable.
the thiophene-containing fused ring group represented by Formula (X-2) is preferably a ring group represented by any one of the following Formulae (X-2a) to (X-2e).
*** represents a binding position to a ring including L w , or another G or T.
the binding positions of these ring groups are not particularly limited, and may be any of the ring-constituting carbon atoms.
the binding positions of the ring groups represented by the respective formulae are all preferably two ring-constituting carbon atoms adjacent to the ring-constituting sulfur atoms in the thiophene ring in the respective formulae.
X is preferably -O-, -S-, -C(R X2c ) 2 -, or -Si(R X2c ) 2 -, and more preferably -C(R x2c ) 2 -, -O-, or -S-.
R X2c represents a hydrogen atom or a substituent. This substituent has the same definition as R T2 , but is preferably an alkyl group.
the thiophene ring group represented by Formula (X-2b), Formula (X-2c), Formula (X-2d), or Formula (X-2e) is preferable; the thiophene ring group represented by Formula (X-2b), Formula (X-2c), or Formula (X-2d) is more preferably; and the thiophene ring group represented by Formula (X-2b) or Formula (X-2c) is particularly preferable.
the thiophene-containing fused ring group represented by Formula (X-3) is preferably a ring group represented by the following Formula (X-3a) or (X-3b), and particularly preferably a ring group represented by the following Formula (X-3b).
X3a to X3c each independently represent -O- or -S-.
X3a is preferably -S-, and X3b and X3c are preferably both -O-.
**** represents a binding position to a ring including L w , or another G or T.
the binding position of the ring group represented by Formula (X-3a) is not particularly limited, and may be any one of the ring-constituting carbon atoms.
the binding positions of the ring groups represented by Formulae (X-3a) and (X-3b) are both preferably the 2- and 5-positions of the thiophene ring.
R T3 represents a substituent.
the substituent has the same definition as R T3 of Formula (X-3), and preferred examples thereof are also the same.
the number PT3a of the substituents R T3 is an integer of 0 to 2, and more preferably 0 or 1. In the present invention, even in a case where the ring group has two substituents R T3 's, it is preferable that the two substituents R T3 's are not bonded to each other to form a ring.
R T3 may be bonded to the thiophene ring in the formula, or may be bonded to a ring having X3a as a ring-constituting atom.
R T3b represents an alkylene group.
the -X3b-R T3b -X3c- group is preferably an alkylenedioxy group.
This alkylenedioxy group has the same definition as the alkylenedioxy group in Formula (X-3), and preferred examples thereof are also the same.
n of G's is an integer of 2 to 7, preferably an integer of 2 to 5, and more preferably 2 or 3.
the combination of the bonded G's is not particularly limited.
the G's to be combined may be the same G's or different G's.
the same G's mean G's in which the thiophene ring structures represented by the respective formulae or thiophene-containing fused ring structures are the same, and also include G's having difference in the presence or absence, the kinds, and the binding positions of substituents.
Preferred examples of the combination of G's include -Formula (X-1a)-Formula (X-1a)-, -Formula (X-1a)-Formula (X-2b)-, -Formula (X-1a)-Formula (X-2c)-, -Formula (X-1a)-Formula (X-2e)-, -Formula (X-1a)-Formula (X-3b)-, -Formula (X-2b)-Formula (X-2b)-, -Formula (X-2b)-Formula (X-3b)-, -Formula (X-2c)-Formula (X-3b)-, -Formula (X-3a)-Formula (X-3b)-, and -Formula (X-3b)-Formula (X-3b)-Formula (X-3b)-.
more preferred examples of the combination of G's include a combination "-(G)n-" of G's in the specific examples of the ligand LA which will be described later, and also include a combination "-(G)n-" of G's contained in the ligand LA in the metal complex dyes D-1 to D-33 synthesized in Examples which will be described later.
the "-(G)n-" in the specific examples of the ligand LA which will be described later and the "-(G)n-” contained in the ligand LA in the metal complex dyes D-1 to D-33 are still more preferable, and the "-(G)n-" contained in the ligand LA in the metal complex dyes D-1 to D-33 is particularly preferable.
T represents a hydrogen atom or a substituent.
the substituent is not particularly limited, but has the same definition as R T1 , preferred examples thereof are the same, and among those, an alkyl group or an alkylthio group is preferable.
the number of the carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and more preferably 1 to 9.
the number of carbon atoms in the alkylthio group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 9, and particularly preferably 1 to 6.
R 1TF to R 4TF each independently represent a hydrogen atom or an alkyl group.
a hydrogen atom or an alkyl group is appropriately selected.
R 1TF , R 2TF , and R 4TF are each a hydrogen atom
R 3TF is an alkyl group
R 1TF and R 3TF are each a hydrogen atom
R 2TF and R 4TF are each an alkyl group
a plurality of alkyl group's may be the same as or different from each other.
the alkyl group that can be contained in R 1TF to R 4TF has the same definition as the alkyl group of R T1 , and is selected from the alkyl groups in the substituent group T R which will be described later' but the number of carbon atoms thereof is preferably 3 to 12, and more preferably 5 to 9.
T represents a hydrogen atom or a substituent, and is as described above.
examples of the amino group include an alkylamino group, an arylamino group, and a heteroarylamino group, in addition to an unsubstituted amino group (-NH 2 ).
the metal complex dye has the ligand LD coordinating to the metal ion M through the nitrogen atom and the anion of a coordinating atom, together with the ligand LA, the heat stability of the photoelectric conversion element or the dye-sensitized solar cell is enhanced, and in particular, high durability as well as high photoelectric conversion efficiency are exhibited.
the ligand LD is preferably a ligand represented by the following Formula (DL).
ma1 and ma4 each independently represent an integer of 0 to 3.
mb is 0, ma represents an integer of 0 to 4, and when mb is 1, ma represents an integer of 0 to 3.
a plurality of R a 's, a plurality of R a1 's, and a plurality of R a4 's may be the same as or different from each other, and they may be bonded to each other to form a ring. Further, R a and R a1 , and R a and R a4 may be linked to each other to form a ring.
Examples of the aromatic ring as a 5- or 6-membered ring in the ring D DL , the ring E DL , and the ring F include an aromatic hydrocarbon ring and an aromatic hetero ring, with an aromatic hetero ring being preferable.
the respective rings of the ring D DL , the ring E DL , and the ring F may be fused with at least one of an aromatic ring and an aliphatic hydrocarbon ring.
a benzene ring is preferable.
the aromatic hetero ring may be any of aromatic rings including the heteroatom as a ring-constituting atom, and is preferably, for examples, a non-fused 6-membered ring, a 6-membered ring fused with a 5-membered ring, a 5-membered ring fused with a benzene ring, or a 6-membered ring fused with a benzene ring, more preferably a non-fused 6-membered ring or a 6-membered ring fused with a 5-membered ring, and still more preferably a non-fused 6-membered ring.
the ring D DL , the ring E DL , and the ring F each include a coordinating atom bonded to the metal ion M.
the coordinating atom is not particularly limited, but is preferably a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, or an anion of any of these atoms.
R a , R a1 , and R a4 examples include a group selected from the substituent group T R which will be described later.
the number of carbon atoms in the respective substituents which can be adopted as R a is not particularly limited, but is preferably the same as the number of carbon atoms in the substituent which can be adopted as R AA , with respect to the same substituent as the substituent which can be adopted as R AA , which will be described later, among the respective substituents which can be adopted as R a , and more preferably, a preferred range of the number of carbon atoms is the same as that of the substituent which can be adopted as R AA .
the number of carbon atoms is the same as the number of carbon atoms in the respective substituents of the substituent group T R which will be described later, and a preferred range thereof is also the same, with respect to a substituent other than the substituent which can be adopted as R AA , which will be described later, among the respective substituents which can be adopted as R a . This also applies to the respective substituents which can be adopted as R a1 or R a4 .
R a , R a1 , and R a4 each have a group R VU represented by the following Formula (V U -1) or (V U -2) as a substituent, and it is particularly preferable that R a has the following group R VU .
T represents an oxygen atom, a sulfur atom, -NR CA -, -C(R CA ) 2 -, or -Si(R CA ) 2 -, and R CA 's each represent a hydrogen atom or a substituent.
R AA represents a substituent, and R AB and R AC each independently represent a hydrogen atom or a substituent.
R BA to R BE each independently represent a hydrogen atom or a substituent, and at least one of R BA , R BB , R BD , or R BE represents a substituent.
the number of the groups R VU contained in the ligand LD may be any number of 1 or more, and is preferably 1 to 3, and more preferably 1 or 2.
T is an oxygen atom, a sulfur atom, -NR CA -, -C(R CA ) 2 -, or -Si(R cA ) 2 -, with a sulfur atom being preferable.
R CA 's each represent a hydrogen atom or a substituent, with a hydrogen atom being preferable.
Examples of the substituent which can be adopted as R CA include a group selected from the substituent group T R which will be described later.
R AA represents a substituent.
the substituent which can be adopted as R AA is not particularly limited, and examples thereof include a group selected from the substituent group T R which will be described later.
the substituent is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an amino group, an alkylamino group, a cycloalkylamino group, an arylamino group, a hetero ring amino group, a silyl group, or a silyloxy group.
the substituent which can be adopted as R AA is more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an amino group, an alkylamino group, a cycloalkylamino group, or an arylamino group, still more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylamino group, a cycloalkylamino group, or an arylamino group, particularly preferably an alkyl group, an alkoxy group, or an alkylamino group, and most preferably an alkyl group or an alkoxy group.
R AA The substituent which can be adopted as R AA is preferably bonded to a thiophene ring (in a case where T is a sulfur atom) in view of photoelectric conversion efficiency.
R AA may further be substituted with a group selected from the substituent group T R which will be described later.
the alkyl group encompasses a linear alkyl group and a branched alkyl group.
the number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 4 to 30, still more preferably 5 to 26, and particularly preferably 6 to 20.
alkyl group examples include methyl, ethyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 3,7-dimethyloctyl, isodecyl, s-decyl, n-dodecyl, 2-butyloctyl, n-hexadecyl, isohexadecyl, n-eicosy, n-hexacosyl, isooctacosyl, trifluoromethyl, and pentafluoroethyl.
the number of carbon atoms in the cycloalkyl group is preferably 3 to 30, more preferably 5 to 30, still more preferably 6 to 26, and particularly preferably 6 to 20.
Examples of the cycloalkyl group include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
the cycloalkyl group may also be fused with an aliphatic ring, an aromatic ring, or a hetero ring.
the alkoxy group encompasses a linear alkoxy group and a branched alkoxy group.
the alkyl moiety of the alkoxy group has the same definition as the alkyl group, and preferred examples thereof are also the same.
Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, 3,7-dimethyloctyloxy, n-decyloxy, isodecyloxy, s-decyloxy, 2-butyloctyloxy, n-dodecyloxy, n-hexadecyloxy, isohexadecyloxy, n-eicosyoxy, n-hexacosyloxy, and isooctacosyloxy.
the cycloalkyl moiety of the cycloalkoxy group has the same definition as the cycloalkyl group, and preferred examples thereof are also the same.
Examples of the cycloalkoxy group include cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
the aryloxy group encompasses a carbocyclic aryloxy group in which an aryl group is an aromatic carbon-based ring (aromatic hydrocarbon ring) group, and a heteroaryloxy group in which an aryl group is an aromatic hetero ring group.
the number of carbon atoms in the aryloxy group is preferably 3 to 30, more preferably 3 to 25, still more preferably 3 to 20, and particularly preferably 3 to 16.
Examples of the aryloxy group include phenoxy, naphthoxy, imidazoyloxy, benzimidazoyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, and thiophen-3-yloxy.
a thiophene ring is preferable.
the alkylthio group encompasses a linear alkylthio group and a branched alkylthio group.
the alkyl moiety of the alkylthio group has the same definition as the alkyl group, and preferred examples thereof are also the same.
alkylthio group examples include methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, t-butylthio, n-pentylthio, n-hexylthio, n-octylthio, 2-ethylhexylthio, 3,7-dimethyloctylthio, n-decylthio, isodecylthio, s-decylthio, n-dodecylthio, 2-butyloctylthio, n-hexadecylthio, isohexadecylthio, n-eicosythio, n-hexacosylthio, and isooctacosylthio.
the cycloalkyl moiety of the cycloalkylthio group has the same definition as the cycloalkyl group, and preferred examples thereof are also the same.
Examples of the cycloalkylthio group include cyclopropylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, and cyclooctylthio.
the arylthio group encompasses a carbocyclic arylthio group in which an aryl group is an aromatic carbon-based ring, and a heteroarylthio group in which an aryl group is an aromatic hetero ring.
the number of carbon atoms in the arylthio group is preferably 3 to 30, more preferably 3 to 25, still more preferably 3 to 20, and particularly preferably 3 to 16.
arylthio group examples include phenylthio, naphthylthio, imidazoylthio, benzimidazoylthio, pyridin-4-ylthio, pyrimidinylthio, quinazolinylthio, purinylthio, and thiophen-3-ylthio.
a thiophene ring is preferable.
the alkylamino group encompasses an N-alkylamino group and an N,N-dialkylamino group, and the number of carbon atoms in the alkyl group is preferably 1 to 30, and more preferably 2 to 30.
Examples of the alkylamino group include ethylamino, diethylamino, 2-ethylhexylamino, bis(2-ethylhexyl)amino, and n-octadecylamino.
the cycloalkylamino group encompasses an N-cycloalkylamino group and an N,N-dicycloalkylamino group.
the cycloalkyl moiety of the cycloalkylamino group has the same definition as the cycloalkyl group, and preferred examples thereof are also the same.
cycloalkylamino group examples include cyclopropylamino, dicyclopropylamino, N-cyclopropyl-N-ethylamino, cyclopentylamino, dicyclopentylamino, N-cyclopentyl-N-methylamino, cyclohexylamino, dicyclohexylamino, cycloheptylamino, and cyclooctylamino.
the arylamino group encompasses a carbocyclic arylamino group in which an aryl group is an aromatic carbon-based ring, and a heteroarylamino group in which an aryl group is an aromatic hetero ring.
the carbocyclic arylamino group encompasses an N-arylamino group, an N-alkyl-N-arylamino group, and an N,N-diarylamino group.
the heteroarylamino group encompasses an N-heteroarylamino group, an N-alkyl-N-heteroarylamino group, an N-aryl-N-heteroarylamino group, and an N,N-diheteroarylamino group.
the heterocyclic amino group is a heterocyclic amino group (aliphatic heterocyclic amino group) other than a heteroarylamino group.
the number of carbon atoms is preferably 0 to 30, more preferably 1 to 25, still more preferably 2 to 20, and particularly preferably 2 to 16.
the ring-constituting heteroatom is preferably selected from an oxygen atom, a sulfur atom, and a nitrogen atom, and in terms of the number of ring members, 5- to 7-membered rings are preferable, and 5- or 6-membered rings are more preferable.
the silyl group encompasses an alkylsilyl group, a cycloalkylsilyl group, an arylsilyl group, an alkyloxysilyl group, a cycloalkyloxysilyl group, and an aryloxysilyl group.
the silyl group is preferably an alkylsilyl group, a cycloalkylsilyl group, or an arylsilyl group.
the number of carbon atoms in the silyl group is preferably 3 to 30, more preferably 3 to 24, still more preferably 3 to 20, and particularly preferably 3 to 18.
silyl group examples include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, cyclohexyldimethylsilyl, triisopropylsilyl, t-butyldiphenylsilyl, methyldimethoxysilyl, phenyldimethoxysilyl, and phenoxydimethylsilyl.
the silyloxy group encompasses an alkylsilyloxy group, a cycloalkylsilyloxy group, and an arylsilyloxy group.
the number of carbon atoms in the silyloxy group is preferably 3 to 30, more preferably 3 to 24, still more preferably 3 to 20, and particularly preferably 3 to 18.
Examples of the silyloxy group include trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy, triisopropylsilyloxy, cyclohexyldimethylsilyloxy, and t-butyldiphenylsilyloxy.
R AB represents a hydrogen atom or a substituent, with a hydrogen atom being preferable.
R AC represents a hydrogen atom or a substituent
R AB and R AC has the same definition as R AA , and preferred examples thereof are also the same.
R AB or R AC is a substituent
the respective substituents of R AA to R AC may be the same as or different from each other.
R BA , R BB , R BD , or R BE is a substituent. It is particularly preferable that at least one or both of R BA and R BE are a substituent, and all of R BB , R BC , and R BD are a hydrogen atom; or at least one or both of R BB and R BD are a substituent, and all of R BA , R BC , and R BE are a hydrogen atom.
two or more substituents may be the same as or different from each other.
ma, ma1, and ma4 are each preferably an integer of 0 to 2, and more preferably 1 or 2.
the ligand represented by Formula (DL) is preferably represented by the following Formula (DL-1) or (DL-2).
R a2 and R a3 each independently represent a substituent not having an acidic group.
ma2 represents 0 or 1, with 1 being preferable.
ma3 represents an integer of 0 to 2, with 1 or 2 being more preferable.
X1 and X2 each independently represent CR a5 or a nitrogen atom.
R a5 represents a hydrogen atom or a substituent. This substituent has the same definition as R a in Formula (DL), and a preferred range thereof is also the same.
a ring including X1 and X2 (also referred to as a ring F) has the same definition as the ring F in Formula (DL), and a preferred range thereof is also the same.
the ring D and the ring E each independently represent an aromatic ring as a 5- or 6-membered ring.
aromatic ring examples include the rings mentioned as the ring D DL and the ring E DL in Formula (DL), and preferred aromatic rings are also the same as the rings mentioned as the ring D DL and the ring E DL .
* represents a coordinating position (binding position) to a metal ion M.
the ring D 2L represents an aromatic ring.
a 111 to A 141 each independently represent an anion of a nitrogen atom or an anion of a carbon atom.
R 111 to R 143 each independently represent a hydrogen atom or a substituent not having an acidic group.
a 111 to A 141 are each an anion of a carbon atom or an anion of a nitrogen atom, in which a hydrogen atom bonded to a nitrogen atom or a carbon atom constituting the ring D 2L is dissociated.
examples of the ring D 2L include an aromatic hydrocarbon ring, an oxygen-containing aromatic hetero ring, a sulfur-containing aromatic hetero ring, and a nitrogen-containing aromatic hetero ring.
the aromatic hydrocarbon ring examples include a benzene ring and a naphthalene ring, among which a benzene ring is preferable, and a benzene ring substituted with a halogen atom, a halogenated alkyl group, or a halogenated aryl group is more preferable.
the halogenated alkyl group is an alkyl group substituted with a halogen atom, with a fluorinated alkyl group (for example, a trifluoromethyl group) being preferable.
a phenyl group substituted with 1 to 5 halogen atoms is preferable.
oxygen-containing aromatic hetero ring a furan ring is preferable, and as the sulfur-containing aromatic hetero ring, a thiophene ring is preferable.
nitrogen-containing aromatic hetero ring a pyrrole ring, a pyrazole ring, an imidazole ring, or a triazole ring is preferable.
Preferred examples of the ring D 2L include the respective rings in which one of ring-constituting atoms of a benzene ring, a thiophene ring, or a furan ring becomes an anion, or the respective rings represented by the following Formulae (a-1) to (a-5), (a-1a), (a-2a), (a-1b), and (a-4a).
Rd represents a substituent not having an acidic group.
b1 represents an integer of 0 to 2
b2 represents an integer of 0 to 3
b3 represents 0 or 1.
the plurality of Rd' s may be the same as or different from each other. Further, a plurality of Rd's may be bonded to each other to form a ring. Examples of Rd include a group selected from the substituent group T R which will be described later.
R 111 to R 143 have the same definitions as R a in Formula (DL), and preferred ranges thereof are also the same.
At least one, and more preferably one or two of R 111 to R 114 , R 121 to R 123 , R 131 to R 133 , and R 141 to R 143 , respectively, are substituents.
the ligand LD is tridentate ligand, it is preferably a tridentate ligand represented by any one of the following Formulae (3L-1) to (3L-4).
the ring D 2L in Formulae (3L-1) to (3L-4) has the same definition as the ring D 2L in Formulae (2L-1) to (2L-4), and a preferred range thereof is also the same.
the ring D 2L is more preferably an aromatic ring including any one of A 211 to A 242 and a carbon atom or an aromatic ring including two carbon atoms.
two ring D 2L 's in the respective formulae may be the same as or different from each other.
R DA1 represents an aryl group (aromatic hydrocarbon ring group) or a heteroaryl group (aromatic hetero ring group), and R DA2 represents an alkyl group, an aryl group, or an aromatic hetero ring group.
R DA1 and R DA2 may be bonded to each other to form a ring.
LL represents an ethenyl group, an ethynyl group, an arylene group, or a heteroarylene group.
a represents an integer of 0 to 5, and when a is 2 or more, LL's present in plural numbers may be the same as or different from each other.
SA The group represented by Formula (SA) is preferably substituted with an aromatic hydrocarbon ring coordinating to the metal ion M or a nitrogen-containing aromatic hetero ring, and more preferably substituted with a nitrogen atom-containing aromatic hetero ring.
R DA1 or R DA2 is an aryl group or a heteroaryl group, and it is more preferable that both of R DA1 and R DA2 are aryl groups.
the aryl group or the heteroaryl group may have a substituent, and examples of such a substituent include a group selected from the substituent group T R which will be described later.
the aryl group is not particularly limited, and examples thereof include a phenyl group and a naphthyl group, with a phenyl group being preferable.
the heteroaryl group is not particularly limited, but is preferably a furanyl group or a thienyl group.
LL may form a fused structure together with an aromatic hydrocarbon ring including a coordinating atom of the ligand or a nitrogen-containing aromatic hetero ring.
LL may be an ethenyl group, and this ethenyl group may be bonded to a nitrogen-containing aromatic hetero ring including a coordinating atom of the ligand to form a quinoline ring.
Examples of the arylene group in LL include a phenylene group and a naphthylene group, and the heteroarylene group is preferably a divalent 5- or 6-membered ring which contains an oxygen atom, a sulfur atom, or a nitrogen atom as a ring-constituting atom, and may be fused with a benzene ring or a hetero ring.
hetero ring of the heteroarylene group examples include a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring, with a furan ring or a thiophene ring being preferable.
the ethenyl group, the arylene group, or the heteroarylene group in LL may have a substituent, and examples of the substituent include a group selected from the substituent group T R which will be described later.
R DA1 and R DA2 are bonded to each other to form a ring.
the ring may have a substituent, and examples of such a substituent include a group selected from the substituent group T R which will be described later.
the ligand represented by Formula (DL) can be synthesized by, for example, the method described in US2010/0258175A1 , JP4298799B , or Angew. Chem. Int. Ed., 2011, 50, pp. 2054-2058 , the methods described in the reference documents listed in these documents, or the methods equivalent thereto.
ligand represented by Formula (DL) examples are shown below. Further, examples of this ligand LD also include the ligand LD in the metal complex dye which will be described later. The present invention is not limited to these ligands LD.
Me represents methyl
* represents a binding position at which rings are bonded to each other, or a pyridine ring and the substituent R 201 are bonded to each other.
the ligand LX may be a monodentate ligand, and is preferably, for example, a group or atom selected from the group consisting of an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, and a halogen atom, or anions thereof.
the ligand LX includes an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, or the like, these groups may or may not have a substituent. Further, in a case where an aryl group, a hetero ring group, a cycloalkyl group, or the like is included, these may or may not have a substituent, and may be a monocycle or a fused ring.
CI represents a counterion when the counterion is necessary for neutralizing the charge of the metal complex dye.
the metal complex dye is cationic or anionic, or whether the metal complex dye has a net ionic charge depends on the metal, the ligand, and the substituent in the metal complex dye.
the metal complex dye When the substituent has a dissociative group or the like, the metal complex dye may have a negative charge arising from dissociation. In this case, an electric charge of the metal complex dye as a whole is electrically neutralized by CI.
the counterion CI is, for example, an inorganic or organic ammonium ion (for example, a tetraalkyl ammonium ion and a pyridinium ion), a phosphonium ion (for example, a tetraalkylphosphonium ion and an alkyltriphenylphosphonium ion), an alkali metal ion (a Li ion, a Na ion, a K ion, and the like), an alkaline earth metal ion, a metal complex ion, or a proton.
an inorganic or organic ammonium ion for example, a tetraalkyl ammonium ion and a pyridinium ion
a phosphonium ion for example, a tetraalkylphosphonium ion and an alkyltriphenylphosphonium ion
an alkali metal ion a
an inorganic or organic ammonium ion (a tetraethylammonium ion, a tetrabutylammonium ion, a tetrahexylammonium ion, a tetraoctylammonium ion, a tetradecylammonium ion, and the like), an alkali metal ion, and a proton are preferable.
the counterion CI is, for example, an inorganic anion or an organic anion.
examples thereof include a hydroxide ion, a halogen anion (for example, a fluoride ion, a chloride ion, a bromide ion, and an iodide ion), a substituted or unsubstituted alkylcarboxylate ion (for example, an acetate ion and a trifluoroacetate ion), a substituted or unsubstituted arylcarboxylate ion (for example, a benzoate ion), a substituted or unsubstituted alkylsulfonate ion (for example, a methanesulfonate ion and a trifluoromethanesulfonate ion), a substituted or unsubstituted arylsulf
an ionic polymer or another dye with an opposite charge from the dye in interest may be used, or a metal complex ion (for example, a bisbenzene-1,2-dithiolatonickel (III)) may also be used.
a metal complex ion for example, a bisbenzene-1,2-dithiolatonickel (III)
a halogen anion a substituted or unsubstituted alkylcarboxylate ion, a substituted or unsubstituted alkylsulfonate ion, a substituted or unsubstituted arylsulfonate ion, an aryldisulfonate ion, a perchlorate ion, and a hexafluorophosphate ion are preferable, and a halogen anion and a hexafluorophosphate ion are more preferable.
the ligand LA, the ligand LD, and the ligand LX are as described above, and the combination of these ligands is not particularly limited.
a preferred combination of the ligands is a combination of the preferred ligand LA, the preferred ligand LD, and the preferred ligand LX.
the metal complex dye represented by Formula (I) is preferably a metal complex dye represented by the following Formula (I-1) or (I-2).
M and LX each have the same definitions as M and LX in Formula (I).
G, T, and n each have the same definitions as G, T, and n in Formula (AL-1).
Anc represents an acidic group, and has the same definition as the acidic group of Formula (AL-1), and preferred examples thereof are also the same.
the ring D and the ring E each independently represent a 5- or 6-membered aromatic ring.
D 1 and D 2 each independently represent an anion of a carbon atom or an anion of a nitrogen atom.
the bond between D 1 and D 2 in the ring D and the ring E, and a carbon atom bonded to a pyridine ring is a single bond or a double bond.
the ring D and the ring E have the same definitions as the ring D and the ring E of Formulae (DL-1) and (DL-2), and preferred examples thereof are also the same.
R a1 to R a4 each independently represent a substituent.
R a1 to R a4 each have the same definitions as R a1 to R a4 of Formulae (DL-1) and (DL-2), and preferred examples thereof are also the same.
ma1, ma2, and ma4 each independently represent an integer of 0 to 3.
ma3 represents an integer of 0 to 4.
ma1 to ma4 each have the same definitions as ma1 to ma4 of Formulae (DL-1) and (DL-2), and preferred examples thereof are also the same.
a plurality of R a1 's to R a4 's may each be bonded to each other to form a ring.
the metal complex dye represented by Formula (I) can be synthesized by, for example, the method described in JP2013-084594A , the method described in JP4298799B , the method described in each specification of US2013/0018189A1 , US2012/0073660A1 , US2012/0111410A1 , and US2010/0258175A1 , the method described in Angew. Chem. Int. Ed., 2011, 50, pp. 2054-2058 , the methods described in the reference documents listed in these documents, the patent documents regarding solar cells, known methods, or the methods equivalent thereto.
the metal complex dye represented by Formula (I) are shown in the following description (including Examples). Further, the specific examples in the following description and the specific examples in Examples also include metal complex dyes in which at least one of -COOH's is formed into a salt of the carboxyl group. In these metal complex dyes, examples of the counter cation that forms a salt of a carboxyl group include the positive ions described for the CI. The present invention is not limited to these metal complex dyes. In a case where these metal complex dyes have optical isomers or geometric isomers, the metal complex dye may be any of these isomers or a mixture of these isomers.
substituents include the groups selected from the following substituent group T R .
the alkyl group in a case where an alkyl group is described as separate from a cycloalkyl group (for example, the description of the substituents which may be adopted as R AA ), the alkyl group is used to mean inclusion of both of a linear alkyl group and a branched alkyl group.
the alkyl group in a case where an alkyl group is not described as separate from a cycloalkyl group (a case where an alkyl group is simply described), and unless otherwise specified, the alkyl group is used to mean inclusion of a linear alkyl group, a branched alkyl group, and a cycloalkyl group.
a group with a linear or branched structure and a group with a cyclic structure may be sometimes separately described for clarification of both groups, as in the alkyl group and the cycloalkyl group.
Examples of the groups included in the substituent group T R include the following groups or the groups formed by the combination of a plurality of the following groups:
Examples of the group selected from the substituent group T R more preferably include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a hetero ring group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an amino group, an acylamino group, a cyano group, and a halogen atom, and particularly preferably include an alkyl group, an alkenyl group, a hetero ring group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a cyano group.
the substituent, or the like when the compound, the substituent, or the like includes an alkyl group, an alkenyl group, or the like, these may be substituted or unsubstituted. Further, when the compound, the substituent, or the like includes an aryl group, a hetero ring group, or the like, these may be a monocycle or a fused ring, and may be substituted or unsubstituted.
the electrically conductive support is not particularly limited as long as it has electrical conductivity and is capable of supporting a photoconductor layer 2 or the like.
the electrically conductive support is preferably an electrically conductive support 1 formed of a material having conductivity, such as a metal, or an electrically conductive support 41 having a glass or plastic substrate 44 and a transparent electrically-conductive film 43 formed on the surface of the substrate 44.
the electrically conductive support 41 in which the transparent electrically-conductive film 43 is formed by applying an electrically conductive metal oxide onto the surface of the substrate 44 is more preferable.
the substrate 44 formed of plastics include the transparent polymer films described in paragraph No. 0153 of JP2001-291534A .
ceramics ( JP2005-135902A ) or electrically conductive resins ( JP2001-160425A ) can be used, in addition to glass and plastics.
the electrically conductive supports 1 and 41 are substantially transparent.
substantially transparent means that the transmittance of light (at a wavelength of 300 to 1,200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more.
the thickness of the electrically conductive supports 1 and 41 is not particularly limited, but is preferably 0.05 ⁇ m to 10 mm, more preferably 0.1 ⁇ m to 5 mm, and particularly preferably 0.3 ⁇ m to 4 mm.
the particle diameter of the semiconductor fine particles 22 is expressed in terms of an average particle size using a diameter when a projected area is converted into a circle, and is preferably 0.001 to 1 ⁇ m as primary particles, and 0.01 to 100 ⁇ m as an average particle size of dispersions.
Examples of the method for coating the semiconductor fine particles 22 on the electrically conductive supports 1 or 41 include a wet method, a dry method, and other methods.
the thickness of the semiconductor layer 45 can be reduced.
the thickness can be adjusted to 8 ⁇ m or less, and to 6 ⁇ m or less.
porphyrin dye examples include the porphyrin dyes described in Angew. Chem. Int. Ed., 49, pp. 1 to 5 (2010 ), or the like
phthalocyanine dye examples include the phthalocyanine dyes described in Angew. Chem. Int. Ed., 46, p. 8358 (2007 ), or the like.
Ru complex dyes As the dye to be used in combination, Ru complex dyes, squarylium cyanine dyes, or organic dyes are preferable.
the ratio of the mass of the metal complex dye represented by Formula (I)/the mass of another dye is preferably 95/5 to 10/90, more preferably 95/5 to 50/50, still more preferably 95/5 to 60/40, particularly preferably 95/5 to 65/35, and most preferably 95/5 to 70/30.
the surface of the semiconductor fine particles 22 may be treated using an amine compound.
the amine compound include pyridine compounds (for example, 4-t-butylpyridine and polyvinylpyridine). These may be used as they are in a case where they are liquids, or may be used in a state where they are dissolved in an organic solvent.
the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include a butanoic acid, a hexanoic acid, an octanoic acid, a decanoic acid, a hexadecanoic acid, a dodecanoic acid, a palmitic acid, a stearic acid, an oleic acid, a linoleic acid, and a linolenic acid.
a preferred co-adsorbent is a compound represented by the following Formula (CA).
R A1 represents a substituent having an acidic group.
R A2 represents a substituent.
nA represents an integer of 0 or more.
R A1 is preferably an alkyl group substituted with a carboxyl group, a sulfo group, or a salt thereof, and more preferably -CH(CH 3 )CH 2 CH 2 CO 2 H or -CH(CH 3 )CH 2 CH 2 CONHCH 2 CH 2 SO 3 H.
R A2 examples include groups selected from the substituent group T R .
an alkyl group, a hydroxyl group, an acyloxy group, an alkylaminocarbonyloxy group, or an arylaminocarbonyloxy group is preferable; and an alkyl group, a hydroxyl group, or an acyloxy group is more preferable.
nA is preferably 2 to 4.
the light-scattering layer is different from the semiconductor layer in that the light-scattering layer has a function of scattering incident light.
the light-scattering layer 46 preferably contains rod-shaped or plate-shaped metal oxide particles.
the metal oxide particles to be used in the light-scattering layer 46 include particles of the chalcogenides (oxides) of the metals.
the thickness of the light-scattering layer is set to 10% to 50% of the thickness of the photoconductor layer 42.
the light-scattering layer 46 is preferably the light-scattering layer described in JP2002-289274A , and the description of JP2002-289274A is preferably herein incorporated by reference.
the charge transfer layers 3 and 47 used in the photoelectric conversion element of the present invention are layers having a function of complementing electrons for the oxidized forms of the dye 21, and are provided between the light-receiving electrode 5 or 40 and the counter electrode 4 or 48.
the charge transfer layers 3 and 47 include electrolytes.
the expression, "the charge transfer layer includes an electrolyte”, is used to inclusion of both of an aspect in which the charge transfer layer consists of only electrolytes and an aspect in which the charge transfer layer consists of electrolytes and materials other than the electrolytes.
Examples of the electrolyte include a liquid electrolyte having a redox pair dissolved in an organic solvent, and a so-called gel electrolyte in which a molten salt containing a redox pair and a liquid having a redox pair dissolved in an organic solvent are impregnated in a polymer matrix.
a liquid electrolyte is preferable.
Examples of the redox pair include a combination of iodine and an iodide (preferably an iodide salt or an iodide ionic liquid, and preferably lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, and methylpropylimidazolium iodide), a combination of an alkylviologen (for example, methylviologen chloride, hexylviologen bromide, and benzylviologen tetrafluoroborate) and a reductant thereof, a combination of a polyhydroxybenzene (for example, hydroquinone and naphthohydroquinone) and an oxidized form thereof, a combination of a divalent iron complex and a trivalent iron complex (for example, a combination of potassium ferricyanide and potassium ferrocyanide), and a combination of a divalent cobalt complex and a trivalent cobal
a nitrogen-containing aromatic cation iodide salt as a 5- or 6-membered ring is additionally used.
a nitrile compound As the organic solvent which is used for a liquid electrolyte, a nitrile compound, an ether compound, an ester compound, or the like is preferable, a nitrile compound is more preferable, and acetonitrile or methoxypropionitrile is particularly preferable.
the counter electrodes 4 and 48 preferably work as a positive electrode in a dye-sensitized solar cell.
the counter electrodes 4 and 48 usually have the same configurations as the electrically conductive support 1 or 41, but in a configuration in which strength is sufficiently maintained, a substrate 44 is not necessarily required.
a preferred structure of the counter electrodes 4 and 48 is a structure having a high charge collecting effect.
At least one of the electrically conductive support 1 or 41 and the counter electrode 4 or 48 should be substantially transparent so that light may reach the photoconductor layers 2 and 42.
the electrically conductive support I or 41 is preferably transparent to allow sunlight to be incident from the side of the electrically conductive support 1 or 41.
the present invention can be applied to the photoelectric conversion elements and the dye-sensitized solar cells described in, for example, JP4260494B , JP2004-146425A , JP2000-340269A , JP2002-289274A , JP2004-152613A , or JP1997-27352A ( JP-H09-27352A ).
the present invention can be applied to the photoelectric conversion elements and the dye-sensitized solar cells described in, for example, JP2000-90989A , JP2003-217688A , JP2002-367686A , JP2003-323818A , JP2001-43907A , JP2005-85500A , JP2004-273272A , JP2000-323190A , JP2000-228234A , JP2001-266963A , JP2001-185244A , JP2001-525108A , JP2001-203377A , JP2000-100483A , JP2001-210390A , JP2002-280587A , JP2001-273937A , JP2000-285977A , or JP2001-320068A .
the photoelectric conversion element and the dye-sensitized solar cell of the present invention are preferably produced using a dye solution (the dye solution of the present invention) which contains the metal complex dye of the present invention and a solvent.
the dye solution of the present invention is preferably one in which the concentrations of the metal complex dye and the co-adsorbent have been adjusted so that the dye solution can be used as it is during production of the photoelectric conversion element or the dye-sensitized solar cell.
the dye solution of the present invention preferably contains 0.001% to 0.1 % by mass of the metal complex dye of the present invention.
the amount of the co-adsorbent to be used is as described above.
the photoconductor layer is preferably formed by applying (including a dip method) the dye solution onto the semiconductor fine particles provided on the electrically conductive support, followed by drying and curing.
the metal complex dye and the synthesis intermediate synthesized in Example 1 were identified by mass spectrum (MS) measurement and 1 H-NMR measurement.
the TBA salt of the synthesized metal complex dye becomes the same mass as the metal complex dye which is electrically neutral by protonization in the MS measurement, and therefore the results of the MS measurement are omitted for the TBA salt.
the synthesized terpyridine compound (an ethyl esterified product of the ligand LA) was identified by MS measurement and 1 H-NMR measurement.
Metal complex dyes D-1 to D-33 synthesized in the present Example are shown below.
a metal complex dye (D-1) and a metal complex dye (D-1TBA) were synthesized.
the compound (1-9) was identified from the following data.
the compound (1-10) (0.6 g), a compound (1-11) (0.32 g), N,N-dimethylformamide (DMF, 10 mL), and tributylamine (1 mL) were put into a 50 mL eggplant flask, and the mixture was heated at 140°C for 3 hours in a nitrogen atmosphere. The reaction mixture was returned to room temperature and then concentrated, and the concentrated residue was purified by silica gel column chromatography to obtain 0.6 g of a compound (1-12).
the compound (1-12) (0.6 g), ammonium thiocyanate (0.42 g), DMF (40 mL), and H 2 O (4 mL) were put into a 50 mL eggplant flask, and the mixture was heated at 100°C for 3 hours. The reaction mixture was returned to room temperature and then concentrated, and the concentrated residue was purified by silica gel column chromatography to obtain 0.3 g of a compound (1-13).
the metal complex dye (D-1) was identified from the following data.
the metal complex dye (D-1) (100 mg) and a 10% tetrabutylammonium hydroxide (TBAOH) methanol solution (0.25 g) were introduced into a 10 mL eggplant flask, and the mixture was allowed to undergo a reaction at room temperature. The obtained solution was concentrated to obtain 100 mg of a metal complex dye (D-1TBA).
TSAOH tetrabutylammonium hydroxide
the synthesized metal complex dyes (D-2) to (D-33) were identified from the data in Table 1 below.
the synthesized AC-1 to AC-6 which are each a diethyl esterified product of a terpyridine compound were identified from the date in Table 2 below. Further, the terpyridine compounds AC-1, AC-5, and AC-6 were also each identified from the 1 H-NMR data shown in Figs. 4 to 6 .
the 1 H-NMR of AC-1 ( Fig. 4 ), AC-5 ( Fig. 5 ), and AC-6 ( Fig. 6 ) which are each a diethyl esterified product of a terpyridine compound was measured with a proton resonance frequency of 400 MHz, each using a CDCl 3 solvent and tetramethylsilane (TMS) as an internal standard substance.
AC-1 which is a diethyl esterified product of a terpyridine compound is the compound (1-9), and was used for the synthesis of the metal complex dye (D-1) and the like.
the visible absorption spectrum of the synthesized metal complex dye (D-1) was measured.
the metal complex dye (D-1) was dissolved in a TBAOH/methanol solution having a concentration of 340 mmol/L to prepare a TBAOH/methanol solution having a concentration of the metal complex dye (D-1) of 17 ⁇ mol/L. This solution was used to measure the light absorption spectrum of the metal complex dye (D-1). "UV-3600” (manufactured by Shimadzu Corporation) was used as a measurement device.
the obtained absorption spectra are shown in Fig. 3 .
the vertical axis indicates a molar light absorption coefficient ⁇ (L/mol ⁇ cm).
the dye-sensitized solar cell 20 (in a scale of 5 mm x 5 mm) shown in Fig. 2 was produced.
the production was carried out in accordance with the procedure shown below.
the following performance of each of the produced dye-sensitized solar cells 20 was evaluated. The results are shown in Tables 3-1 and 3-2.
An electrically conductive support 41 was manufactured in which a fluorine-doped SnO 2 electrically-conductive film (transparent electrically-conductive film 43, film thickness of 500 nm) was formed on a glass substrate (substrate 44, thickness of 4 mm). Further, a titania paste "18NR-T" (manufactured by DyeSol) was screen-printed on the SnO 2 electrically-conductive film, followed by drying at 120°C. Then, the dried titania paste "18NR-T” was screen-printed again, followed by drying at 120°C for 1 hour. Thereafter, the dried titania paste was calcined at 500°C in air to form a semiconductor layer 45 (layer thickness; 10 ⁇ m).
a titania paste "18NR-AO" manufactured by DyeSol was screen-printed on this semiconductor layer 45, followed by drying at 120°C for 1 hour. Then, the dried titania paste was calcined at 500°C to form a light-scattering layer 46 (layer thickness; 5 ⁇ m) on the semiconductor layer 45.
each of light-receiving electrodes 40 having the respective metal complex dyes carried on the light-receiving electrode precursor [A] was manufactured.
a platinum electrode (thickness of a thin film with Pt; 100 nm) having the same shape and size as those of the electrically conductive support 41 was manufactured as a counter electrode 48. Further, 0.1 M (mol/L) of iodine, 0.1 M of lithium iodide, 0.5 M of 4-t-butylpyridine, and 0.6 M of 1,2-dimethyl-3-propylimidazolium iodide were dissolved in acetonitrile to prepare a liquid electrolyte as an electrolytic solution. Further, a Spacer-S "SURLYN" (trade name, manufactured by DuPont), which has a shape matching to the size of the photoconductor layer 42, was prepared.
SURLYN spacer-S "SURLYN" (trade name, manufactured by DuPont), which has a shape matching to the size of the photoconductor layer 42, was prepared.

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EP15818813.6A 2014-07-07 2015-07-01 Photoelektrisches umwandlungselement, farbstoffsensibilisierte solarzelle, metallkomplexfarbstoff, farbstofflösung und terpyridin-verbindung oder veresterungsprodukt davon Not-in-force EP3168847B1 (de)

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JP2014140079		2014-07-07
JP2015039390		2015-02-27
PCT/JP2015/068977 WO2016006512A1 (ja)	2014-07-07	2015-07-01	光電変換素子、色素増感太陽電池、金属錯体色素、色素溶液、およびターピリジン化合物またはそのエステル化物

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JP2012146632A (ja) *	2010-12-21	2012-08-02	Sony Corp	色素、色素増感光電変換素子、電子機器および建築物
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- 2015-07-01 WO PCT/JP2015/068977 patent/WO2016006512A1/ja not_active Ceased
- 2015-07-01 EP EP15818813.6A patent/EP3168847B1/de not_active Not-in-force
- 2015-07-01 CN CN201580032074.6A patent/CN106463274B/zh not_active Expired - Fee Related
- 2015-07-01 JP JP2016532896A patent/JP6204591B2/ja active Active
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TW201609704A (zh)	2016-03-16
CN106463274A (zh)	2017-02-22
US20170117099A1 (en)	2017-04-27
KR20170016441A (ko)	2017-02-13
WO2016006512A1 (ja)	2016-01-14
CN106463274B (zh)	2018-09-07
JP6204591B2 (ja)	2017-09-27
JPWO2016006512A1 (ja)	2017-06-01
EP3168847A4 (de)	2017-05-31
KR101982944B1 (ko)	2019-05-27
EP3168847B1 (de)	2018-05-16
US20190295778A1 (en)	2019-09-26

Publication	Publication Date	Title
EP2922137B1 (de)	2019-04-03	Fotoelektrisches umwandlungselement, farbstoffsensibilisierte solarzelle, metallkomplexfarbstoff, farbstofflösung, farbstoffadsorbierte elektrode und verfahren zur herstellung einer farbstoffsensibilisierten solarzelle
US20190295778A1 (en)	2019-09-26	Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, and terpyridine compound or esterified product thereof
EP3168848B1 (de)	2019-05-22	Fotoelektrisches umwandlungselement, farbstoffsensibilisierte solarzelle, metallkomplexfarbstoff, farbstofflösung und terpyridinverbindung oder veresterungsprodukt daraus
US20170092434A1 (en)	2017-03-30	Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, and dye solution
US20170092435A1 (en)	2017-03-30	Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, and terpyridine compound or esterified product thereof
JP6300333B2 (ja)	2018-04-04	光電変換素子、色素増感太陽電池、金属錯体色素、色素溶液、およびターピリジン化合物またはそのエステル化物
JP6300334B2 (ja)	2018-03-28	光電変換素子、色素増感太陽電池、金属錯体色素および色素溶液
EP3270391A1 (de)	2018-01-17	Fotoelektrisches umwandlungselement, farbstoffsensibilisierte solarzelle, metallkomplexfarbstoff und farbstofflösung
WO2016052196A1 (ja)	2016-04-07	光電変換素子、色素増感太陽電池、金属錯体色素、色素溶液、およびターピリジン化合物またはそのエステル化物
JP6304612B2 (ja)	2018-04-04	光電変換素子、色素増感太陽電池、金属錯体色素および色素溶液

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